Liquid crystalline 3,4:9,10-perylenetetacarbocylic acid diimides

ABSTRACT

Perylene-3,4:9,10-tetracarboxylic diimides of the general formula  
                 
 
     where  
     R 1 , R 2 , R 3  and R 4  are independently hydrogen, chlorine, bromine or substituted or unsubstituted aryloxy, arylthio, arylamino, hetaryloxy or hetarylthio;  
     R 5 , R 6 , R 7 , R 8 , R 9  and R 10  are independently hydrogen or long-chain alkyl, alkoxy or alkylthio whose carbon chain may in each case contain up to four double bonds, with the proviso that at least four of these radicals are not hydrogen  
     are prepared and used as liquid-crystalline materials for electronic, optoelectronic and photonic applications, for coloration of macromolecular organic and of inorganic materials, as fluorescent dyes and as laser dyes and also as organic materials for solar collectors and electroluminescence applications.

DESCRIPTION

[0001] The present invention relates to novelperylene-3,4:9,10-tetracarboxylic diimides (hereinafter referred to asperylimides for short) of the general formula I

[0002] where

[0003] R¹, R², R³ and R⁴ are independently hydrogen, chlorine, bromineor substituted or unsubstituted aryloxy, arylthio, arylamino, hetaryloxyor hetarylthio;

[0004] R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen orlong-chain alkyl, alkoxy or alkylthio whose carbon chain may in eachcase contain up to four double bonds, with the proviso that at leastfour of these radicals are not hydrogen.

[0005] The invention also relates to the preparation of theseperylimides and to their use as liquid-crystalline materials forelectronic, optoelectronic and photonic applications, for coloration ofmacromolecular organic and of inorganic materials, as fluorescent dyesand as laser dyes and also as organic materials for solar collectors andelectroluminescence applications.

[0006] There are a multiplicity of technological applications, forexample charge transport material applications, where the materials usedhave to have not only suitable molecular properties such as color andemission but also a supramolecular order, which is customarilydetermined by the relationship of the molecules in the crystal.

[0007] Particularly interesting arrangements of functional molecules areobtained in liquid-crystalline phases, which have substantial advantagesin use over pigmentary solids. For instance, the mobility of themolecules in the liquid-crystalline phase makes it possible to preparefilms of uniform thickness and of a macroscopic order induced by thesubstrate. When low viscosities are desired for the production process,films may also be prepared by raising the temperature above the meltingpoint. On the other hand, liquid-crystalline orders which are stableover wide temperature ranges are also obtainable by attaching thermallyor photochemically crosslinkable groups.

[0008] Perylimides have hitherto formed the basis for the followingliquid-crystalline compounds:

[0009] Chem. Mater. 10, 1309-1319 (1998) describes perylimides which arederivatized at the imide nitrogen atoms with oligoethyleneoxysubstituents as mesogenic groups. However, these groups tend to absorbatmospheric humidity, so that thin films of the liquid-crystalline phasein particular are not morphologically stable.

[0010] Angew. Chem. 110, 1463-1467 (1998) concerns liquid-crystallinecoronenediimides which, however, form columnar liquid-crystalline phasesonly at above 150° C. and are preparable from perylene derivatives onlyby means of inconvenient processes.

[0011] EP-A-422 535 describes liquid-crystalline polymers which arepartly functionalized with perylimide units in the side chains; that is,are not intrinsically liquid-crystalline low molecular weight dyes.

[0012] WO-A-97/22607 and 94/25504 disclose perylimides which are1,7-disubstituted or 1,6,7,12-tetrasubstituted in the perylenestructure, but which differ from the claimed perylimides of the formulaI not least by the substitution on the imide nitrogen atoms and are notliquid crystalline.

[0013] It is an object of the present invention to provide furtherliquid-crystalline dyes having advantageous application properties.

[0014] We have found that this object is achieved by the perylimides ofthe formula I defined at the beginning.

[0015] Preferred perylimides of the formula I are disclosed in thesubclaims.

[0016] The invention also provides a process for preparing theseperylimides, which comprises reacting aperylene-3,4:9,10-tetracarboxylic dianhydride of the general formula II

[0017] with identical or different primary amines of the generalformulae III

[0018] in the presence of a polar aprotic solvent and of an imidationcatalyst.

[0019] The invention further provides a process for preparingperylene-3,4:9,10-tetracarboxylic diimides of the general formula Ia

[0020] where Ar is substituted or unsubstituted aryloxy, arylthio,hetaryloxy or hetarylthio, which comprises reacting1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboxylic dianhydride (IIa)with identical or different primary amines of the general formulae III

[0021] in the presence of a polar aprotic solvent and of an imidationcatalyst and reacting the resultant1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboxylic diimides of thegeneral formula I′

[0022] with an aromatic alcohol or thioalcohol of the general formula IV

H—Ar  IV

[0023] in the presence of an inert aprotic solvent and of anon-nucleophilic or only minimally nucleophilic base.

[0024] The invention further provides a process for preparingperylene-3,4:9,10-tetracarboxylic diimides of the general formula Ib

[0025] where Ar is substituted or unsubstituted aryloxy, arylthio,hetaryloxy or hetarylthio, which comprises reacting1,7-dibromoperylene-3,4:9,10-tetracarboxylic dianhydride (IIb) withidentical or different primary amines of the general formulae III

[0026] in the presence of a polar aprotic solvent and of an imidationcatalyst and reacting the resultant1,7-dibromoperylene-3,4:9,10-tetracarboxylic diimides of the generalformula I″

[0027] with an aromatic alcohol or thioalcohol of the general formula IV

H—Ar  IV

[0028] in the presence of an inert aprotic solvent and of anon-nucleophilic or only minimally nucleophilic base.

[0029] The invention further provides for the use of the perylimides ofthe formula I as liquid-crystalline materials in electronic,optoelectronic or photonic applications, for coloration ofmacromolecular organic and of inorganic materials, as fluorescent dyesand as laser dyes and also as organic materials for solar collectors andelectroluminescence applications.

[0030] The variables in the formula I will now be more particularlydescribed.

[0031] Examples of nonhydrogen radicals R¹ to R⁴ are chlorine, bromine,phenoxy, phenylthio, phenylamino, 2-naphthyloxy, 2-naphthylthio, 2-, 3-and 4-pyridyloxy, 2-, 3- and 4-pyridylthio, 2-, 4- and 5-pyrimidyloxyand 2-, 4- and 5-pyrimidylthio, of which chlorine and bromine arepreferred and phenoxy is particularly preferred.

[0032] When the perylene structure is to be substituted, preferably allor just two (especially 1,7-substitution) of the radicals R¹ to R⁴ areidentical ones of the abovementioned radicals. Aryl and hetaryl may eachbear up to three, preferably one or two, substituents.

[0033] Examples of these substituents are:

[0034] methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl,heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, tert-octyl, nonyl,isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl andeicosyl (the above designations isooctyl, isononyl, isodecyl andisotridecyl are trivial names derived from the alcohols obtained in theoxo process), of which C₁-C₈-alkyl radicals and especially tert-butylare preferred;

[0035] 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl,2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl,4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl,4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl,3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl and3,6,9,12-tetraoxatetradecyl;

[0036] 2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl,2-isopropylthioethyl, 2-butylthioethyl, 2- and 3-methylthiopropyl, 2-and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthiobutyl, 2-and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl,4,8-dithianonyl, 3,7-dithiaoctyl, 3,7-dithianonyl, 4,7-dithiaoctyl,4,7-dithianonyl, 2- and 4-butylthiobutyl, 4,8-dithiadecyl,3,6,9-trithiadecyl, 3,6,9-trithiaundecyl, 3,6,9-trithiadodecyl,3,6,9,12-tetrathiatridecyl and 3,6,9,12-tetrathiatetradecyl;

[0037] 2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2-and 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl,6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl,3,6-dimethyl-3,6-diazaoctyl, 9-methyl-3,6,9-triazadecyl,3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyland 3,6,9,12-tetramethyl-3,6,9,12-tetraazatridecyl;

[0038] propan-2-on-1-yl, butan-3-on-1-yl, butan-3-on-2-yl and2-ethylpentan-3-on-1-yl;

[0039] 2-methylsulfonylethyl, 2-ethylsulfonylethyl,2-propylsulfonylethyl, 2-isopropylsulfonylethyl, 2-butylsulfonylethyl,2- and 3-methylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and3-propylsulfonylpropyl, 2- and 3-butylsulfonylpropyl, 2- and4-methylsulfonylbutyl, 2- and 4-ethylsulfonylbutyl, 2- and4-propylsulfonylbutyl and 4-butylsulfonylbutyl;

[0040] carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl,5-carboxypentyl, 6-carboxyhexyl, 8-carboxyoctyl, 10-carboxydecyl,12-carboxydodecyl and 14-carboxytetradecyl;

[0041] methylcarboxymethyl, ethylcarboxymethyl, propylcarboxymethyl,butylcarboxymethyl, pentylcarboxymethyl, hexylcarboxymethyl,methyl-2-carboxyethyl, ethyl-2-carboxyethyl, propyl-2-carboxyethyl,butyl-2-carboxyethyl, pentyl-2-carboxyethyl, hexyl-2-carboxyethyl,methyl-3-carboxypropyl, ethyl-3-carboxypropyl, propyl-3-carboxypropyl,butyl-3-carboxypropyl, pentyl-3-carboxy-propyl, hexyl-3-carboxypropyl,methyl-4-carboxybutyl, methyl-5-carboxypentyl, methyl-6-carboxyhexyl,methyl-8-carboxyoctyl, methyl-10-carboxydecyl, methyl-12-carboxydedecyland methyl-14-carboxytetradecyl;

[0042] sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl,5-sulfopentyl, 6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl,12-sulfododecyl and 14-sulfotetradecyl;

[0043] methylsulfomethyl, ethylsulfomethyl, propylsulfomethyl,butylsulfomethyl, pentylsulfomethyl, hexylsulfomethyl,methyl-2-sulfoethyl, ethyl-2-sulfoethyl, propyl-2-sulfoethyl,butyl-2-sulfoethyl, pentyl-2-sulfoethyl, hexyl-2-sulfoethyl,methyl-3-sulfopropyl, ethyl-3-sulfopropyl, propyl-3-sulfopropyl,butyl-3-sulfopropyl, pentyl-3-sulfopropyl, hexyl-3-sulfopropyl,methyl-4-sulfobutyl, methyl-5-sulfopentyl, methyl-6-sulfohexyl,methyl-8-sulfooctyl, methyl-10-sulfodecyl, methyl-12-sulfododecyl andmethyl-14-sulfotetradecyl;

[0044] 2-hydroxyethyl, 2- and 3-hydroxypropyl, 1-hydroxyprop-2-yl, 2-and 4-hydroxybutyl, 1-hydroxybut-2-yl and 8-hydroxy-4-oxaoctyl;

[0045] 2-cyanoethyl, 3-cyanopropyl, 2-methyl-3-ethyl-3-cyanopropyl,7-cyano-7-ethylheptyl and 4-methyl-7-methyl-7-cyanoheptyl;

[0046] methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,sec.-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy,tert-pentyloxy, hexyloxy and 2-methylpentyloxy;

[0047] cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, morpholinyl,pyrrolidinyl and piperidyl.

[0048] Examples of particularly preferred substituted aromatic radicalsR¹ to R⁴ are 4- and 3-tert-butylphenoxy, 4-cyclohexylphenoxy,4-propoxyphenoxy, 4-butoxyphenoxy, 4-hexyloxyphenoxy and1,1,3,3-tetramethylbutylphenoxy.

[0049] At least four of the radicals R⁵ to R¹⁰ which substitute into thephenyl radicals on the imide nitrogen atoms are not hydrogen, andpreferably two phenyl radicals each bear two of the nonhydrogensubstituents. Both 3,5- and 3,4-disubstitution are possible. Preferably,however, all radicals R⁵ to R¹⁰ are not hydrogen. And they may beidentical or different. Preferably, however, at least the radicalssitting on any one phenyl radical are identical. Particular preferenceis given to perylimides of the formula I where the two phenyl radicalsbear the same substituents.

[0050] The alkyl chains of the radicals R⁵ to R¹⁰ may be linear orbranched and generally have 8 to 20, preferably 10 to 14, carbon atoms.

[0051] In addition to the alkyl radicals already mentioned above, thefollowing alkoxy and alkylthio radicals may be mentioned as suitable forthe radicals R⁵ to R¹⁰ by way of example:

[0052] octyloxy, 2-ethylhexyloxy, isooctyloxy, nonyloxy, isononyloxy,decyloxy, isodecyloxy, undecyloxy, dodecyloxy, tridecyloxy,tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy,nonadecyloxy and eicosyloxy;

[0053] octylthio, 2-ethylhexylthio, isooctylthio, nonylthio,isononylthio, decylthio, isodecylthio, undecylthio, dodecylthio,tridecylthio, tetradecylthio, pentadecylthio, hexadecylthio,heptadecylthio, octadecylthio, nonadecylthio and eicosylthio.

[0054] In addition, the alkyl chains of the radicals R⁵ to R¹⁰ maycontain one to four, especially three, double bonds. Of theseunsaturated radicals, especially those radicals are suitable that arederived from naturally occurring terpene hydrocarbons and terpenealcohols and from the alcohols of unsaturated fatty acids. Particularlysuitable alkenyloxy radicals are formed for example by geraniol, nerol,linalool and citronellol and also the alcohols of oleic acid, linoleicacid and linolenic acid.

[0055] Examples of particularly preferred phenyl substituents on theimide nitrogen atoms are 3,4,5-tridodecyloxyphenyl,3,4,5-tridecyloxyphenyl, 3,5- and 3,4-didodecyloxyphenyl.

[0056] The inventive perylimides of the formula I are advantageouslypreparable by the similarly inventive process by reacting thesubstituted or unsubstituted perylene-3,4:9,10-tetracarboxylicdianhydrides of the formula II with identical or different primaryamines of the formulae III in the presence of a polar aprotic solventand of an imidation catalyst.

[0057] Useful polar aprotic solvents include in particular aproticnitrogen heterocycles, such as pyridine, pyrimidine, imidazole,quinoline, isoquinoline, quinaldine, N-methylpiperidine,N-methylpiperidone and N-methylpyrrolidone, carboxamides, such asdimethylformamide and dimethylacetamide, and tetraalkylureas, such astetramethylurea, of which quinoline is particularly preferred.

[0058] The amount of solvent is not critical per se. From 5 to 120 g ofsolvent may be used per g of perylene-3,4:9,10-tetracarboxylicdianhydride (II).

[0059] Useful imidation catalysts include in particular Lewis-acidicsalts of organic and inorganic acids with metals such as zinc, iron,copper and magnesium and also the oxides of these metals, for examplezinc acetate, zinc propionate, zinc oxide, iron(II) acetate, iron(III)chloride, iron(II) sulfate, copper(II) acetate, copper(II) oxide andmagnesium oxide, of which zinc acetate is particularly preferred. Itwill be appreciated that mixtures of the catalysts mentioned may also beused. Preferred amounts of metal catalyst range from about 20 to 100 mol%, based on (II).

[0060] It is also possible to use the acids themselves, for exampleorganic acids, especially C₁-C₃-carboxylic acids such as formic acid,acetic acid and propionic acid, and inorganic acids such as phosphoricacid, each preferably in very concentrated form, as imidation catalysts.The acids here also act as solvents or as a cosolvent and are thereforecustomarily used in excess.

[0061] The molar ratio of primary amine (III) to aperylene-3,4:9,10-tetracarboxylic dianhydride (II) is customarily in therange from about 2:1 to 4:1, preferably in the range from about 2.2:1 to3:1.

[0062] The reaction temperature is generally in the range from 60 to250° C., preferably in the range from 100 to 230° C., particularlypreferably in the range from 160 to 200° C.

[0063] It is advisable to conduct the reaction under a protective gasatmosphere (preferably argon or else nitrogen).

[0064] It is generally not necessary to employ superatmospheric pressurein the case of this inventive process.

[0065] The reaction customarily ends in from 1 to 4 h.

[0066] An advantageous procedure is as follows:

[0067] Perylene-3,4:9,10-tetracarboxylic dianhydride (II), solvent andcatalyst are initially charged, the amine (III) is added at roomtemperature with stirring, the apparatus is purged with argon for about10 min, and the stirred mixture is heated to the reaction temperatureand maintained at that temperature for from about 2 to 3 h. Aftercooling to room temperature, the reaction product is filtered off andwashed with water and then with an aliphatic alcohol such as methanol.

[0068] The product may be purified by recrystallization (e.g., −5dissolving in an organic solvent such as dichloromethane andreprecipitating with an aliphatic alcohol such as methanol) or by columnchromatography (e.g., silica gel/dichloromethane).

[0069] When the perylene-3,4:9,10-tetracarboxylic dianhydride (II) is tobe reacted with two different amines (IIIa) and (IIIb), the reaction isadvantageously carried out in stages, by using first the amine (IIIa) inan amount of from about 0.8 to 1 mol per mole of (II) and, after theformation of the monoimide has ended, the amine (IIIb) in an amount offrom about 1 to 2 mol per mole of (II) to form the diimide (cf. Adv.Mater. 11, 754-758 (1999)).

[0070] This inventive process advantageously provides the perylimides ofthe formula I in high purity (generally ≧95%) and good yield (generallyin the range from 60 to 95%).

[0071] The perylene-3,4:9,10-tetracarboxylic dianhydrides (II) used asstarting materials for this inventive preparative process are known perse or are preparable by known methods starting from1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboxylic dianhydride (IIa)or 1,7-dibromoperylene-3,4:9,10-tetracarboxylic dianhydride (IIb) (cf.WO-A-97/22607 and EP-A-227 980).

[0072] A further way to prepare the (het)aryloxy- and(het)arylthio-substituted perylimides of the formulae Ia and Ibcomprises as per the further inventive processes a first step ofreacting 1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboxylicdianhydride (IIa) or 1,7-dibromoperylene-3,4:9,10-tetracarboxylicdianhydride (IIb) with identical or different primary amines of theformulae III in the presence of a polar aprotic solvent and of animidation catalyst and further reacting the resultant1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboxylic diimides of theformula I′ or 1,7-dibromoperylene-3,4:9,10-tetracarboxylic diimides ofthe formula I″ in a second step with an aromatic (thio)alcohol of theformula IV in the presence of an inert aprotic solvent and of anon-nucleophilic or only minimally nucleophilic base.

[0073] The first step of this inventive preparative process may becarried out similarly to the above-described process. The second step ofthis preparative process, which may be carried out as described inWO-A-97/22607, usefully employs as the inert aprotic solvent inparticular nitrogen heterocycles such as pyridine, pyrimidine,quinoline, isoquinoline, quinaldine and especially N-methylpyrrolidoneas inert aprotic reaction medium.

[0074] The amount of solvent is not critical per se. Typically from 10to 50 g, preferably from 25 to 35 g, of solvent are used per g ofperylimide of the formula I′ or I″.

[0075] Preferred bases include alkali metal hydroxides, e.g., sodiumhydroxide and potassium hydroxide, and especially alkali metalcarbonates, e.g., sodium carbonate and potassium carbonate.

[0076] Generally from 2 to 3, preferably from 2.2 to 2.5, molequivalents of base are used per mole of perylimide of the formula I′ orI″.

[0077] The molar ratio of aromatic (thio)alcohol (IV) to perylimide ofthe formula I′ or I″ is generally in the range from 2:1 to 3:1,preferably in the range from 2.0:1 to 2.2:1.

[0078] The reaction temperature is customarily in the range from 60 to180° C., especially in the range from 80 to 140° C.

[0079] It is again advisable to employ a protective gas atmosphere.

[0080] The reaction customarily ends in from 1 to 5 h, especially infrom 1 to 2 h.

[0081] An advantageous procedure for this second step is as follows:

[0082] A stirred suspension of perylimide (I′) or (I″), (thio)alcohol(IV) and base in the solvent is initially charged and heated to thereaction temperature under a protective gas over from 1 to 2 h. Aftercooling to room temperature, the reaction mixture is discharged intoabout 3 times the volume of a dilute inorganic acid, for example 5-10%by weight hydrochloric acid, the precipitated reaction product isfiltered off, washed neutral with water and dried under reducedpressure.

[0083] Generally the perylimides of the formula Ia or Ib thus obtainedare already ≧95% pure, so that there is no need for furtherpurification. In the event that additional purification is desired,however, this additional purification may be carried out as in the caseof the further preparative process already described.

[0084] The inventive perylimides of the formula I form stableliquid-crystalline phases and so are very useful for a multiplicity ofapplications, especially for electronic, optoelectronic and photonicapplications, for example as charge transport materials in luminescentdiodes and photovoltaic diodes, photoconductors and transistors. Theyare also useful as fluorescent dyes for coloration of macromolecularorganic materials (e.g., polyolefins) and of inorganic materials and aslaser dyes. They are useful not least as organic materials for solarcollectors and for electroluminescence applications, for example indisplays.

EXAMPLES

[0085] A) Preparation of Inventive Perylimides

Example 1

[0086]N,N′-Di(3,4,5-tridodecyloxyphenyl)perylene-3,4:9,10-tetra-carboxylicdiimide:

[0087] A mixture of 0.12 g (0.3 mmol) ofperylene-3,4:9,10-tetracarboxylic dianhydride, 0.58 g (0.9 mmol) of3,4,5-tridodecyloxyaniline, 0.04 g (0.2 mmol) of zinc acetate and 12 mlof quinoline was heated at 180° C. under argon for 3 h.

[0088] After cooling to room temperature, the reaction mixture waspoured into 100 ml of 1 N hydrochloric acid with stirring. The redprecipitate obtained was filtered off with suction and washed with waterand then with methanol. The product was then purified by dissolving indichloromethane and precipitating with methanol and dried at 70° C.under medium vacuum.

[0089] This provided 0.44 g of a 99% pure product, which corresponds toa yield of 89%.

[0090] Analytical Data:

[0091] Elemental analysis for C₁₀₈H₁₆₂N₂O₁₀ (1648.5) (% by weightcalc./obs.):

[0092] C: 78.69/78.50; H: 9.91/9.81; N: 1.70/1.62;

[0093] 1H NMR (200 MHz, CDCl₃, 25° C., TMS): δ=8.54 (d, 3J (H, H)=7.8Hz, 4H; H2, 5, 8, 11), 8.21 (d, 3J (H, H)=7.8 Hz, 4H; H1, 6, 7, 12),6.63 (s, 4H; ArH), 4.03 (t, 4H; OCH₂), 3.86 (t, 8H; OCH₂), 1.76 (m,12H), 1.6-1.2 (m, 108H), 0.85 (m, 18H) ppm; UV/Vis (CH₂Cl₂): λ_(max) (ε)527 (89 600), 490 (59 500), 459 nm (22 300 mol⁻¹ dm³ cm⁻¹).

Example 2

[0094]N,N′-Di(3,4,5-tridodecyloxyphenyl)-1,7-di(4-tert-butylphenoxy)-perylene-3,4:9,10-tetracarboxylicdiimide:

[0095] Example 1 was repeated, except that 0.34 g (0.5 mmol) of1,7-di(4-tert-butylphenoxy)perylene-3,4:9,10-tetracarboxylic dianhydrideand 0.97 g (1.5 mmol) of 3,4,5-tridodecyloxyaniline and 0.05 g (0.3mmol) of zinc acetate were used.

[0096] The dark red product was purified by column chromatography oversilica gel using dichoromethane.

[0097] This provided 0.58 g of a 99% pure product, which corresponds toa yield of 60%.

[0098] Analytical Data:

[0099] Elemental analysis for C₁₂₈H₁₈₆N₂O₁₂ (1944.6) (% by weightcalc./obs.):

[0100] C: 79.05/79.00; H: 9.64/9.77; N: 1.44/1.49;

[0101] 1H NMR (200 MHz, CDCl₃, 25° C., TMS): δ=9.52 (d, 3J (H, H)=8.4Hz, 2H; H6, 12), 8.53 (d, 3J (H, H)=8.4 Hz, 2H; H5, 11), 8.27 (s, 2H;H2, 8), 7.47 (d, 3J (H, H)=8.7 Hz, 4H; H3′), 7.10 (d, 3J (H, H)=8.7 Hz,4H; H2′), 6.52 (s, 4H; ArH), 4.00 (t, 4H; OCH₂), 3.83 (t, 8H; OCH₂),1.74 (m, 12H), 1.6-1.2 (m, 108H), 1.36 (s, 18H; tert-Bu), 0.87 (m, 18H)ppm;

[0102] UV/Vis (CH₂Cl₂): λ_(max) (ε)=546 (57 500), 511 (39 600), 402 nm(11 600 mol⁻¹ dm³ cm⁻¹).

Example 3

[0103]N,N′-Di(3,4,5-tridodecyloxyphenyl)-1,6,7,12-tetraphenoxyperylene-3,4:9,10-tetracarboxylicdiimide

[0104] Example 1 was repeated, except that 0.19 g (0.25 mmol) of1,6,7,12-tetraphenoxyperylene-3,4:9,10-tetracarboxylic dianhydride, 0.48g (0.75 mmol) of 3,4,5-tridodecyloxyaniline, 0.04 g (0.2 mmol) of zincacetate and 10 ml of quinoline were used.

[0105] The purple precipitate was purified similarly to Example 2.

[0106] This provided 0.35 g of a 99% pure product, which corresponds toa yield of 69%.

[0107] Analytical Data:

[0108] Elemental analysis for C₁₃₂H₁₇₈N₂O₁₄ (2016.9) (% by weightcalc./obs.):

[0109] C: 78.61/78.40; H: 8.90/9.02; N: 1.39/1.40;

[0110] 1H NMR (400 MHz, CDCl₃, 25° C., TMS): δ=8.22 (s, 4H; H2, 5, 8,11), 7.25 (t, 3J (H, H)=8.0 Hz, 8H; H3′), 7.10 (t, 3J (H, H)=7.4 Hz, 4H;H4′), 6.95 (d, 3J (H, H)=8.1 Hz, 8H; H2′), 6.41 (s, 4H; ArH), 3.99 (t,4H; OCH₂), 3.89 (t, 8H; OCH₂), 1.76 (m, 12H), 1.5-1.2 (m, 108H), 0.87(m, 18H) ppm;

[0111] UV/Vis (CH₂Cl₂): λ_(max) (ε)=574 (51 500), 535 (32 500), 445 nm(16 400) (mol⁻¹ dm³ cm⁻¹).

Example 4

[0112]N,N′-Di(3,4,5-tridodecyloxyphenyl)-1,6,7,12-tetra(4-tert-butyl-phenoxy)perylene-3,4:9,10-tetracarboxylicdiimide:

[0113] Example 1 was repeated, except that 0.25 g (0.25 mmol) of1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-tetra-carboxylicdianhydride, 0.48 g (0.75 mmol) of 3,4,5-tridodecyloxyaniline, 0.04 g(0.2 mmol) of zinc acetate and 10 ml of quinoline were used.

[0114] This provided 0.52 g of a 98% pure product, which corresponds toa yield of 92%.

[0115] Analytical Data:

[0116] Elemental analysis for C₁₄₈H₂₁₀N₂O₁₄ (2241.3) (% by weightcalc./obs.):

[0117] C: 79.31/78.91; H: 9.44/9.27; N: 1.25/1.27;

[0118] 1H NMR (200 MHz, CDCl₃, 25° C., TMS): δ=8.23 (s, 4H; H2, 5, 8,11), 7.24 (d, 3J (H, H)=8.7 Hz, 8H; H3′), 6.86 (d, 3J (H, H)=8.7 Hz, 8H;H2′), 6.41 (s, 4H; ArH), 3.98 (t, 4H; OCH₂), 3.89 (t, 8H; OCH₂), 1.75(m, 12H), 1.6-1.2 (m, 108H), 1.26 (s, 36H; tert.Bu), 0.87 (m, 18H) ppm;

[0119] UV/Vis (CH₂Cl₂): λ_(max) (ε)=580 (42 500), 542 (28 000), 452 nm(15 800 mol⁻¹ dm³ cm⁻¹)

[0120] B) Investigation of the Properties of the Perylimides Prepared

Example 5

[0121] Characterization of the Liquid-Crystalline Properties of thePerylimide of Example 1:

[0122] A sample of the compound was heated to above the clear point of376° C. and then cooled down slowly. Under a polarizing microscope, theformation of a spherulitic texture typical of columnar mesophases wasobserved with large pseudoisotropic regions, using crossed polarizers.Although the sample became glassy at lower temperatures, no furtherphase transition was detectable under the polarizing microscope or elseby DSC (heating/cooling rate: 10° C./min). On renewed heating, thetexture remained intact up to the clear point regardless of the heatingrate.

[0123] The wide angle X-ray diffractogram (WAXS; Cu—Kα, Ni-filtered) ofa sample cooled to room temperature exhibited a sharp reflex at 2θ=3.14°and a diffuse halo at 2θ=20°. An additional diffraction experiment on anoriented sample showed a hexagonal arrangement of the first orderreflexes and thus suggested a disordered hexagonal discotic mesophaseD_(hd) having a lattice constant of 32.5 Å and one molecule per columnsegment.

Example 6

[0124] Characterization of the Liquid-Crystalline Properties of thePerylimide of Example 4:

[0125] A sample of the compound was heated to above the clear point of346° C. and then cooled down slowly. Under a polarizing microscope, theformation of a spherulitic texture typical of columnar mesophases wasobserved with large pseudoisotropic regions, using crossed polarizers.Although the sample became glassy at lower temperatures, no furtherphase transition was detectable under the polarizing microscope or elseby DSC (heating/cooling rate: 10° C./min). On renewed heating, thetexture remained intact up to the clear point regardless of the heatingrate.

[0126] The wide angle X-ray diffractogram (WAXS; Cu—Kα, Ni-filtered) ofa sample cooled to room temperature exhibited two sharp reflexes at2θ=3.570 and 2θ=6.12° and a diffuse halo at 2θ=20° suggesting adisordered hexagonal discotic mesophase D_(hd) having a lattice constantof 28.7 Å and one molecule per column segment.

Example 7

[0127] Characterization of the Fluorescence Properties of the Perylimideof Example 4:

[0128] Intensive fluorescence with a peak emission at 616 nm wasobserved in dichloromethane. The fluorescence quantum yield determinedfor an 8·10⁷ molar solution was 21%.

[0129] In aliphatic solvents such as methylcyclohexane, substantialaggregation was observed at high concentrations not only in theabsorption but also in the emission spectra. The absorption maximumshifted to longer wavelengths by 19 nm and the emission maximum by 40nm, which is believed to be due to excitonic interactions of theaggregated chromophores (J-aggregate). Nonetheless, an almost lineardependence on the concentration was observed for the intensity offluorescence.

[0130] The fluorescence spectrum of a film of the compound deposited onquartz glass was almost identical with those obtained for concentratedsolutions and similarly showed a red color with intensive fluorescence.

We claim:
 1. Perylene-3,4:9,10-tetracarboxylic diimides of the generalformula I

where R¹, R², R³ and R⁴ are independently hydrogen, chlorine, bromine orsubstituted or unsubstituted aryloxy, arylthio, arylamino, hetaryloxy orhetarylthio; R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are independently hydrogen orlong-chain alkyl, alkoxy or alkylthio whose carbon chain may in eachcase contain up to four double bonds, with the proviso that at leastfour of these radicals are not hydrogen. 2.Perylene-3,4:9,10-tetracarboxylic diimides as claimed in claim 1 of theformula I where R¹, R², R³ and R⁴ are independently hydrogen, chlorine,bromine or phenoxy which may be substituted by up to three of thefollowing substituents: C₁-C₂₀-alkyl whose carbon chain may beinterrupted by one or more moieties selected from the group consistingof —O—, —S—, —NR¹¹—, —CO— and —SO₂— and/or which may be substituted byone or more substituents selected from the group consisting of —COOR¹¹,—SO₃R¹¹, hydroxyl, cyano, C₁-C₆-alkoxy, C₅-C₈-cycloalkyl and a 5- to7-membered heterocyclic radical which is attached by a nitrogen atom andwhich may contain further heteroatoms; C₁-C₆-alkoxy; cyano; hydroxyl;halogen; nitro, —COOR¹¹ or —SO₃R¹¹; R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ areindependently C₈-C₂₀-alkyl, C₈-C₂₀-alkoxy or C₈-C₂₀-alkylthio whosecarbon chain may in each case contain up to four double bonds; R¹¹ ishydrogen or C₁-C₆-alkyl.
 3. Perylene-3,4:9,10-tetracarboxylic diimidesas claimed in claim 1 of the formula I where R¹, R², R³ and R⁴ areindependently hydrogen or phenoxy which may be monosubstituted byC₁-C₈-alkyl; R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are each C₁₀-C₁₄-alkyl.
 4. Aprocess for preparing perylene-3,4:9,10-tetracarboxylic diimides of theformula I as set forth in any of claims 1 to 3, which comprises reactinga perylene-3,4:9,10-tetracarboxylic dianhydride of the general formulaII

with identical or different primary amines of the general formulae III

in the presence of a polar aprotic solvent and of an imidation catalyst.5. A process for preparing perylene-3,4:9,10-tetracarboxylic diimides ofthe general formula Ia

where Ar is substituted or unsubstituted aryloxy, arylthio, hetaryloxyor hetarylthio, which comprises reacting1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboxylic dianhydride (IIa)with identical or different primary amines of the general formulae III

in the presence of a polar aprotic solvent and of an imidation catalystand reacting the resultant1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboxylic diimides of thegeneral formula I′

with an aromatic alcohol or thioalcohol of the general formula IVH—Ar  IV in the presence of an inert aprotic solvent and of anon-nucleophilic or only minimally nucleophilic base.
 6. A process forpreparing perylene-3,4:9,10-tetracarboxylic diimides of the generalformula Ib

where Ar is substituted or unsubstituted aryloxy, arylthio, hetaryloxyor hetarylthio, which comprises reacting1,7-dibromoperylene-3,4:9,10-tetracarboxylic dianhydride (IIb) withidentical or different primary amines of the general formulae III

in the presence of a polar aprotic solvent and of an imidation catalystand reacting the resultant 1,7-dibromoperylene-3,4:9,10-tetracarboxylicdiimides of the general formula I″

with an aromatic alcohol or thioalcohol of the general formula IVH—Ar  IV in the presence of an inert aprotic solvent and of anon-nucleophilic or only minimally nucleophilic base.
 7. The use ofperylene-3,4:9,10-tetracarboxylic diimides of the formula I as set forthin any of claims 1 to 3 as liquid-crystalline materials for electronic,optoelectronic and photonic applications.
 8. The use ofperylene-3,4:9,10-tetracarboxylic diimides of the formula I as set forthin any of claims 1 to 3 for coloration of macromolecular organic and ofinorganic materials, as fluorescent dyes and as laser dyes.
 9. The useof perylene-3,4:9,10-tetracarboxylic diimides of the formula I as setforth in any of claims 1 to 3 as organic materials for solar collectorsand electroluminescence applications.